Polymerization products of gamme butylenes



p The heating of the sulphuric acid solution for moms Dec. @1932 UNITEDST TES. PATENT ornca MARTIN MUELLER-OUNRADI, 01' L'U'DWIGfilT-THE-RHINE,AND FRITZ EGGEBT,

OF HANNHEIM, GERMANY, ASBIGNOBQ TO I. G. IABBENIITDUSTBIE AKTIENGE-SELLSCEAI'T, 01F nmxroa'r-on-rna-nm, GEBIANY, A CORPORATION 01! GER-MANY ronm'narzarron raonuors or 7 nu'nnnnas 80 Drawing. Application fledJune 14, 1889,!eria1 1T0. 571,0", and in Germany August 7, 1928.,

This invention relates to improvements in the manufacture andproduction'of polymerization products of -butylenes. We have found thatpolymerization prodacts, and in particular dimers besides only smalluantlties of trimers and higher polymerlzation products of y-butylenes,for example of -butylene itself or of its homologues such astrimethylethylene are obtained in good yields in an advantageous mannerby treating the said 11' drocarbons or ases containing the same witcomparative- Ty strong, about from 50 to per cent sulphuric acid,thereupon heating the sulp uric acid solution obtained, for example, toabout 106 centigrade. After removing the pol merization products whichseparate out oring the heating, t e sulphuricacid may he cooled, ifdesired, and again be employed for the treatment of a further quantitycit hydro= carbons.

The treatment of the said hydrocarhons is usually completed in acomparatively short time, and is dependent on the concentration of theacid employed. Thus for example, in the case of the can loyment of anacid of as per cent strength t 18 treatment may take, for example about12 minutes, whereas when an acid of per cent strength is employed ittakes about i minutes. at she-old he understood that the periods givenare only intend ed to denote the relative duration when employinodifferent concentration of acids under otherwise like conditions and notthe absolnte durations of the treatment. The solutiondis usually heatedto about 10G centiera e,

a The adsorption of the hydrocarhons by means of the sulphuric acid canhe carried out at ordinary pressure or at elevated pressures.

the purpose of polymerizing the hydrocarhons is preferably carried outby allowing the solution to flow through a heated tubular systern, inwhich it is advantageous to arrange for the solution which is to heheated to act as thecooling agent for the sulphuric acid which has beenfreed from reaction products and which is to be cooled.

The following example will further illustrate the nature of the saidinvention but the invention is not restricted thereto.

Emample A gas containng about 10 per cent of yhutylene, about 4 per centof 'trimethyl ethylene besides small amounts of other hutylenes andamylenes, 40 per cent of butane;

20 per cent of pentane, 15 per cent of hydrogen, 6 per cent of methaneand other hydrocarbons is passecl' through a washing tower through whichan approximately 55 per cent sulphuric acid solution is trickling insuch a manner that the ma or portion of the hydrocarbons is absorbed loythe sulphuric acid. The solution is then heated "to about centigrade,for example in a tubular Worm, in

- which it enters at the bottom, The polymerination of the hydrocarbonsthen proceeds in such a manner that the polymerization prodnot separatesout as oil consisting of about 80 per cent of dimers and about 20 percent of higher polymers, in particnla-r tr liners oil y-ouztylenctrimethyl ethylene, Alter separation oil the polymerization products thesulphuric acid is cooled and aeain passed through the washing toner,

in a similar manner, instead of the mixture e a t .5 enzatlon productswhich separate out during the heating, cooling the remainin sulphuricacid and employing it over again for the ireatnient oi a furtherquantity of a -hntyone.

2. A process for the production of dimers oi y-bntylenes, besides onlysmall quantities of triiners and higher polymerization prodnets, whichcomprises treating a y-hutylene with a sulphuric acid of between aboutso and 80 per cent strength, thereupon heating 2 r 1,ese,es2

the sulphuric acid solution to about 100 0., removing the0lymerizationproducts which separate out urmg the heating, cooling the remainingsulphuric acid and emplogiui it 5 over. again for thetreatment of a urtor quantity of a -butylene.

3. A process for the production of "dimers of -butylenes, besides onlysmall quantities of trimers and higher polymerization products, which.comprises treating a -butylene with a sulphuric acid of between about50and 60 per cent strength, and thereupon heating the sulphuric acidsolution.

4. A process for the production of dimers :5 of -butylenes, besides onlysmall uantities of trimers and higher polymerization prod: ucts, whichcomprises treating a -butylene with a sulphuric acid of between about50- and 60 per cent strength and thereupon heating the sulphuric acidsolution. to about In testimony whereof wehave hereunto set our hands.

MARTIN MUELLER-CUNRADI.

FRITZ EGGERT.

